Anisotropic copoly(imide oxetane) coatings and articles of manufacture, copoly(imide oxetane)s containing pendant fluorocarbon moieties, oligomers and processes therefor

ABSTRACT

Copoly(imide oxetane) materials are disclosed that can exhibit a low surface energy while possessing the mechanical, thermal, chemical and optical properties associated with polyimides. The copoly(imide oxetane)s are prepared using a minor amount of fluorinated oxetane-derived oligomer with sufficient fluorine-containing segments of the copoly(imide oxetane)s migrate to the exterior surface of the polymeric material to yield low surface energies. Thus the coatings and articles of manufacture made with the copoly(imide oxetane)s of this invention are characterized as having an anisotropic fluorine composition. The low surface energies can be achieved with very low content of fluorinated oxetane-derived oligomer. The copolymers of this invention can enhance the viability of polyimides for many applications and may be acceptable where homopolyimide materials have been unacceptable.

CROSS-REFERENCE TO RELATED APPLICATION

This patent application is a divisional of and the claims the benefit ofpriority to U.S. Non-Provisional patent application Ser. No. 15/819,916,filed Nov. 21, 2017, which is a divisional of and claims the benefit ofand priority to U.S. Non-Provisional patent application Ser. No.13/286,715, filed Nov. 1, 2011, which claims the benefit of and priorityto U.S. Provisional Application No. 61/469,204, filed Mar. 30, 2011,each of the foregoing applications is hereby incorporated by referencein its entirety.

STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH AND DEVELOPMENT

This invention was made in part with Government support. The Governmentmay have certain rights in this invention.

FIELD OF THE INVENTION

This invention pertains to copoly(imide oxetane)s having low adhesionsurface properties and to oligomers useful to make such copoly(imideoxetane)s. The oxetane oligomers contain fluorocarbon moieties thatenable the copoly(imide oxetane)s to achieve the low adhesion surfaceproperties with relatively low oxetane content. The invention alsopertains to processes for making the copoly(imide oxetane)s andanisotropic coatings and articles of manufacture from them.

BACKGROUND TO THE INVENTION

Marine biofouling, membrane fouling, insect adhesion on aircraftsurfaces, microbial contamination of sterile environments, and surfaceparticle contamination all present unique challenges. An array ofmitigations strategies has been pursued to address these problems.

Passive strategies for minimizing fouling or contamination of surfacesare beneficial especially in environments where active mitigation of thefouling or contamination is impractical or impossible. For instance,lunar dust compromised seals, clogged filters, abraded visors and spacesuit surfaces, and was a significant health concern during the Apollomissions. Accordingly, passive mitigation utilizing materials with anintrinsic resistance to surface contamination would be advantageous forsuch applications. One passive mitigation strategy is modification of amaterial's surface energy either chemically or topographically or both.

Any surface material needs to meet the requirements of its application.High performance polymeric materials have been developed to addressvarious requirements for mechanical, thermal, and optical properties.Modification of the chemical constituency of these polymeric materialscan alter their properties. Thus, modification of high performancepolymeric materials is often hampered due to degradation of the desiredcharacteristic properties. Modifying a polymeric material to influencesurface characteristics is problematic as addition of sufficientmodifier to the bulk chemical composition to achieve the desired surfacemodification could also result in the diminution of other importantperformance properties of the polymeric material. If the modifier iswell dispersed within the polymer matrix, a majority of the modifierwill be located in the interior of the polymeric structure where it willnot contribute to the structure's surface properties. This is especiallyproblematic if the modifier is expensive, provides no other performanceenhancement or diminishes bulk properties of the polymeric material.

Polymeric materials with low adhesion surface properties have beendemonstrated to be effective in a wide variety of applications. Lowsurface energy polymeric materials, i.e., those exhibiting a high watercontact angle, have been used to reduce marine biofouling, water and iceadhesion, and biofilm formation; to improve oxidation, corrosion andstain resistance; to minimize dust adhesion; and to modify theperformance of microfluidic systems and biomedical devices. The abilityto selectively modify the surface energy of high performance polymericmaterials without sacrificing their superior mechanical, thermal andoptical properties is of significant utility.

A number of approaches have been suggested to yield polymeric materialswith low surface energy. One of the most well known polymeric materialshaving low surface energy are fluorinated, aliphatic polymers such asthose available under the trade name TEFLON® fluoropolymers. Thepresence of both aliphatic carbon species and fluorine atoms contributesto the low surface energy of this class of materials. These polymericmaterials have an approximate homogeneous composition, do not use acontrolled modification, and thus cannot be tailored for theintroduction of further surface features. Moreover, they do not adherewell to substrates and are difficult to process. Generally the polymeris provided as a powder to be coated and sintered onto the substrate.Another approach is to vapor deposit highly fluorinated carbonaceousmaterials to various substrates.

Another approach to provide low surface energy polymeric materials is toincorporate surface modifying agents into the materials. These surfacemodifying agents are thermodynamically driven to migrate to the surfaceof the polymeric material preferentially due to more favorableinteractions at the air interface compared to the polymeric matrix.

Omnova Solutions Inc. offers a family of hydroxyl terminatedoxetane-derived oligomers under the trade name POLYFOX® fluorochemicalsand have found commercial application in polymeric systems.Fluorine-containing oxetane derivatives have been used extensively assurface modification agents for modification of urethanes. See, forinstance, Malik, et al., United States patent application publicationNo. US 2004/0087759. Medsker, in U.S. Pat. No. 7,022,801 and Thomas, etal., in United States patent application publication No. 2003/0092862,disclose the use of fluoro-containing oxetane polymers to impartwetting, flow or leveling properties to a variety of coatings whileproducing little foam.

Wynne, U.S. Pat. No. 7,396,590 and Wynne, et al., in U.S. Pat. No.7,771,793 disclose making polymeric articles or coatings that have asurface phase having an activity of interest. They disclose preparing asurface active telechelic that includes both a surface active segmerwhich favors migration to the surface of a bulk polymer and one or morefunctional segmers which provide an activity of interest (e.g., biocide,bioactive, UV protective, hydrophobic, hydrophylic, etc.). Thetelechelics disclosed include those made using fluorine-containingoxetanes.

Weinert, et al, in U.S. Pat. No. 6,972,317 disclose monofunctionalpolyfluorooxetane oligomers and polymers that can be reacted with cyclicethers or functionalized with a functional end group such as anacrylate, a methacrylate, an allylic, an amine, etc., for use inradiation curable or thermal curable coating compositions. They believethat the fluorinated side groups of the fluorooxetanes aredisproportionately present at the interfaces between the coating andsubstrate and between the coating and the atmosphere.

Polyimides are known for their thermal stability, fire resistance, goodchemical resistance and excellent mechanical properties. Polyimides havegood mechanical elongation and tensile strength and good adherenceproperties to many substrates. Some polyimides exhibit high opticalclarity. Polyimides have found application as coatings, insulating filmsin the electronic industry, fibers and articles of manufacture includingfor demanding applications such as bushings, bearings in jet engines, orother constructive parts.

Accordingly, a need exists for a low surface energy polymeric materialthat has the mechanical, thermal, chemical and optical propertiesassociated with polyimides.

SUMMARY

In accordance with this invention copoly(imide oxetane) materials areprovided that can possess the mechanical, thermal, chemical and opticalproperties associated with polyimides and exhibit a low energy surface.By this invention, copoly(imide oxetane)s are prepared using a minoramount of an amino terminated fluorinated oxetane-derived oligomer.Sufficient fluorine-containing segments of the copoly(imide oxetane)smigrate to the exterior surface of the polymeric material to afford lowsurface energies. In preferred copoly(imide oxetane) coatings andarticles of manufacture, the surface is saturated with fluoro-groupseven at very low, e.g., below about 0.5 mass percent oxetane oligomer inthe copoly(imide oxetane). Although greater amounts of oxetane oligomercould be used, often virtually no further improvement in surfacehydrophobicity is observed. Hence it is possible with the copoly(imideoxetane)s of this invention to tailor the surface properties while stillmaintaining the physical properties of the polyimide. The copoly(imideoxetane)s of this invention can enhance the viability of polyimides formany applications and may be acceptable where homopolyimide materialshave been unacceptable.

In the way of an overview, the copoly(imide oxetane)s of this inventionare characterized as containing divalent radicals of an oligomer derivedfrom a fluorine-containing oxetane, preferably oxetanes containing aperfluorinated carbon on a substituent on the beta carbon of theoxetane. The oxetane oligomer content of the copolymer is often lessthan about 10 or 15, preferably less than about 1, mass percent of thecopolymer. In the some preferred aspects, the oxetane oligomer contentof the copolymer is between 0.001 and 0.1, mass percent of thecopolymer. Often the water contact angle is greater than about 85°,preferably greater than about 90°. If desired, concentrations higherthan 15 mass percent oxetane oligomer may be used to make thecopoly(imide oxetane). Although at these high levels of oxetane content,physical properties of the copolymer such as glass transitiontemperature, tensile strength and abrasion resistance will be inferiorto the corresponding polyimide; however, the copoly(amic acid oxetane)and copoly(imide oxetane) will have low surface energy and in someinstances, the copolymer may be soluble in polar organic solvents suchas dimethylacetamide, acetone, and tetrahydrofuran or combinationsthereof.

One aspect of the invention pertains to oligomers represented by theformula:(E)^(y)R¹—C(O)—O-J-C(O)—R¹(E)_(y)wherein:

-   -   J is [CH₂—CR²R³—CH₂—O]_(m) or    -   [(CH₂—CR²R³—CH₂—O)_(p)—(R⁶—O)_(q)—(CH₂—CR²R³—CH₂—O)_(r)—]        wherein R⁶ is a substituted or unsubstituted aliphatic or        aromatic moiety of 2 to 16 carbons, preferably CR⁷CH₂— wherein        R⁷ is H or methyl;    -   E is —NO₂ or —NH₂, and preferably each E is either —NO₂ or —NH₂;    -   y is 1 or 2, and preferably each y is 1;    -   R¹ is an aliphatic or aromatic hydrocarbon moiety of 1 to 10        carbon atoms, preferably R¹ is a divalent phenyl group;    -   R² is —H, —F, or alkyl of 1 to 6 carbon atoms, and preferably is        an alkyl of 1 to 3 carbon atoms, and most often methyl;    -   R³ is —F, —R⁴H_((n-a))F_(a), —R⁵—O—R⁴H_((n-a))F_(a), or        —O—R⁴H_((n-a))F_(a), wherein R⁴ is an alkyl or ether moiety of 1        to 30 carbons, R⁵ is an alkyl moiety of 1 to 30 carbons, a is an        integer of 3 to n, and n is twice the number of carbon atoms in        the alkyl moiety plus 1; and m is between about 4 and 500,        preferably between about 6 and 100, p is between about 4 and        150, q is between about 1 and 150, preferably between about 4        and 150.        Preferably the omega carbon of R⁴ has three fluoride        substituents. Preferably, R⁵ is —CH₂—O—C(R′)₂—CF₃, wherein R′ is        —H or —F.

Preferred oligomers of this invention are represented by the formula:(E)_(y)R¹—C(O)—O-Q_(p)-(R⁶)_(q)-Q_(r)-C(O)—R¹(E)_(y)wherein:

-   -   E, y, R⁶, p, q, r and R¹ are as defined above; and    -   Q is derived from the oligomerization of oxetane monomer    -   wherein at least 40 mole percent of the oxetane monomer is        substituted at the beta carbon with at least one substituent        containing at least one perfluorinated carbon atom.

The substituted oxetane monomer from which Q is derived can berepresented by the formula:

wherein:

-   -   R³ is —F, —R⁴H_((n-a))F_(a), —R⁵—O—R⁴H_((n-a))F_(a), and        —O—R⁴H_((n-a))F_(a), wherein R⁴ is an alkyl or ether moiety of 1        to 30 carbons, and preferably is an alkyl of 1 to 3 carbon        atoms, and most often methyl, R⁵ is an alkyl moiety of 1 to 30        carbons, a is an integer of 3 to n, and n is twice the number of        carbon atoms in the alkyl moiety plus 1.

Another aspect of this invention pertains to polyamic acids that can beimidized to make copoly(imide oxetane)s having the structure representedby:-(G-A)-(D-A)-wherein:

-   -   G is represented by the formula        —NH—R¹—C(O)—O-J-C(O)—R¹—HN—    -   wherein:        -   R¹ and J are as defined above;    -   A is represented by the formula

-   -   wherein:        -   L is a hydrocarbyl-containing moiety of 2 to 100 carbon            atoms optionally containing divalent radicals selected from            the group consisting of oxygen, silyl, sulfur, carbonyl,            sulfonyl, phosphonyl, perfluoro, tertiary amino, and imido;    -   D is represented by the formula        —NH—Z—NH—    -   wherein:        -   Z is a hydrocarbyl-containing moiety of 1 to 100 carbon            atoms optionally containing divalent radicals selected from            the group consisting of oxygen, sulfur, silyl, carbonyl,            sulfonyl, phosphonyl, perfluoro, tertiary amino, and imido.

Another aspect of this invention pertains to copoly(imide oxetane)scontaining the oxetane oligomers of this invention. The copoly(imideoxetane)s are prepared by using the oxetane oligomers of this inventionwherein E is —NH₂, and generally the copoly(imide oxetane) contains lessthan about 10, say, 0.001 to 5, preferably, 0.001 to 0.1, mass percentof the oxetane oligomer. The copoly(imide oxetane)s of this inventioncan be represented by the structure:-(G-M)-(D-M)-wherein:

-   -   G is represented by the formula        ═N—R¹—C(O)—O-J-C(O)—R¹—N═    -   wherein:        -   R¹, and J are as defined above;    -   M is represented by the formula        (—C(O))₂-M-(C(O)—)₂    -   wherein:        -   L is as defined above;    -   D is represented by the formula        ═N—Z—N═    -   wherein:        -   Z is defined as above.            The copoly(imide oxetane) may be a block co-polymer or a            random co-polymer.

A yet further aspect of this invention pertains to coatings having anouter surface and a bonding surface that comprise the copoly(imideoxetane)s of this invention. The coatings are characterized as having ananisotropic distribution of fluorine atoms over its thickness with ahigher concentration at the outer surface. Preferred coatings have awater contact angle of at least 90° at the outer surface. The coatingmay be on any suitable surface including metal, ceramic, glass, wood,paper, fibers, textiles, membranes, or polymer surfaces. The coatingscan be prepared by applying on a substrate a solution containing acopoly(amic acid oxetane) of this invention in a volatile solvent forthe copoly(amic acid oxetane) to form a copoly(amic acidoxetane)-containing coating, and then subjecting the copoly(amic acidoxetane)-containing coating to drying and imidization conditions to formthe anisotropic copoly(imide oxetane)-containing coating. In someaspects, the copoly(imide oxetane) of this invention may be soluble in alow boiling solvent in an imide form, thus allowing for it to be castdirectly on an article and then solvent evaporated to form the coating.

Another aspect of this invention pertains to articles of manufacturehaving an outer surface on a polymeric matrix comprising thecopoly(imide oxetane) of this invention wherein the article ofmanufacture has a higher concentration of fluorine atoms at its outersurface than that used to make the polymeric matrix. The article may bemade by casting, molding, extruding or other suitable process. Forexample, the article of manufacture may be made by forming a polymericmatrix containing the copoly(amic acid oxetane) of this invention intothe shape of the article of manufacture and subjecting the article ofmanufacture to imidization conditions to form the article ofmanufacture. The polymeric matrix may be in a slurry or solvent whenformed into the sought shape or may be in the form of a substantiallydry particulate, e.g., having a major dimension of between about 20 and2000 microns. The particulate polymeric matrix may be formed into thesought shape under pressure and subjected to imidization conditions toform the copoly(imide oxetane)-containing article of manufacture.

An aspect of this invention pertains to making coatings and articles ofmanufacture by contacting a polyamic acid coating or article ofmanufacture with a diamine oligomer of this invention or a copoly(amicacid oxetane) of this invention at its exterior surface and thensubjecting the coating or article of manufacture to imidizationconditions. The polyamic acid coating or article of manufacture need notcontain fluorine, yet upon imidization, the fluorine-containing oxetaneoligomer or copoly(imide oxetane) becomes integral with the material ofthe coating or article of manufacture without gross phase segregation.

An additional aspect of the invention pertains to processes for makingcopoly(amic acid oxetane)s and copoly(imide oxetane)s comprising:

-   -   a. reacting an oxetane oligomer of the formula        H—O-J-H    -   wherein J is as defined above, with an acyl reagent of the        formula O₂N—R¹C(O)X, wherein R¹ is aliphatic or aromatic        hydrocarbon moiety of 1 to 10 carbon atoms and X is selected        from the group consisting of bromide, chloride and iodide, —H,        —OH, and —OR⁸, wherein R⁸ is alkyl of 1 to 3 carbon atoms, under        nucleophilic reaction conditions, to provide nitro-terminated        oligomer;    -   b. hydrogenating the nitro-terminated oligomer under        hydrogenation conditions including the presence of hydrogenation        catalyst to convert nitro moieties to amine moieties and provide        diamine-terminated oligomer;    -   c. reacting the diamine-terminated oligomer with at least one of        -   (i) dianhydride of the formula            O(C(O))₂-L-(C(O))₂O  (I)        -   wherein L is as defined above; preferably in the presence of            one or more diamines of the formula            —NH—Z—NH—  (II)        -   wherein: Z is as defined above, and        -   (ii) anhydride-terminated prepolymer of (I) and (II)            preferably having a weight average molecular weight of            between about 1000 and 500,000 g/mol,    -   under condensation polymerization conditions, to provide the        polyamic acid; and    -   d. subjecting the polyamic acid to imidization conditions,        preferably either a thermal ring closure including a temperature        of at least about 120° C., say, between 150° C. to 400° C., to        provide the polyimide, or a chemical ring closure in the        presence of dehydrating and ring-closing catalyst such as one or        more of pyridine, triethylamine, acetic anhydride or the like at        a temperature in the range of about −20° C. to 200° C.

A yet further aspect of this invention comprises a polymer composite,which may be in the form of a coating or article of manufacture, saidcomposite comprising copolymer containing fluoro-containing oxetaneoligomer and a particulate filler to provide a water contact angle of atleast 100°. Examples of copolymers include, but are not limited to,block and random copolymers such as polyester/polyoxetane copolymerssuch as from ethylene terephthalate, propylene terephthalate,trimethylene terephthalate and butylene terephthalate; acryliccopolymers such as copoly(acrylate oxetane), copoly(methacrylateoxetane); copoly(urethane oxetane); copoly(amide oxetane) such as frombutyrolactam, caprolactam, lauryl lactam, and polyamides from thereaction of adipic acid or sebacic acid with a diamine such ashexamethylene diamine; copoly(imide oxetane); copoly(siloxane oxetane);copoly(urea oxetane); copoly(ether oxetane) such as copolymers withpolyether ether ketone; copoly(sulfone oxetane); and copoly(sulfideoxetane). The preferred copoly(imide oxetane)s are those of thisinvention. The particulate fillers may be composed of metal, metaloxides and metal sulfides. Preferably the particulate fillers have amajor dimension of less than about 5 microns, more preferably less thanabout 0.5 micron, and sometimes less than about 0.05 micron. Examples ofparticulate fillers include, but are not limited to, oxides such assilica, alumina, titania, yttria, zirconia, molybdenum oxide, ironoxide, metals and metal alloys such as gold, silver, copper, germanium,platinum, iron and cobalt/platinum; semiconductors such a lead sulfide,cadmium sulfide, CdSe, CdTe; sulfides such as molybdenum sulfide andcesium sulfide; phosphates such as aluminum phosphate; clays such asmontmorillonite, vermiculite, hectorite; carbonates such as calciumcarbonate; carbon black, finely ground rubber, and molecular sieves. Theamount of filler can vary depending upon particle size and inherentsurface energy. In general, the composites contain from about 0.1 to 40,say, 0.5 to 20, mass percent particulate filler based upon the mass ofthe composite. In preferred aspects of this invention, the compositepossesses a water contact angle of at least about 120°.

DETAILED DISCUSSION Definitions and Procedures

Water contact angle as used herein is the angle that deionized watercontacts the surface of the polymer. A FTA 1000B contact anglegoniometer available from First Ten Angstroms, Inc., Portsmouth, Va.,United States can be used to measure the water contact angle using an 8milliliter drop.

Polyimides

Polyimides are typically prepared by the reaction between a diamine anda dianhydride under condensation polymerization conditions although itis possible to prepare polyimides by other reactions such as that of adianhydride and a diisocyanate or a diester of the dianhydride with adiamine. The copoly(imide oxetane)s of this invention use as all or aportion of the diamine component a diamine which is a derivative of afluorine-containing oxetane oligomer, herein called a FOX diamine.

The FOX diamine preferably constitutes a minor portion by mass of thediamine components used in the synthesis, often less than about 20,preferably less than about 10, and most times between about 0.02 to 0.5,mass percent of the total diamine where the properties of the polyimideare sought. Generally, the amount of FOX diamine is sufficient toprovide a water contact angle of at least 85°, preferably at least 90°.

The FOX diamine can be represented by the structure:—N—R¹—C(O)—O-J-C(O)—R¹—N—as discussed above. One or more FOX diamines can be contained in thecopoly(imide oxetane)s of this invention.

The optional diamine may be one or more aliphatic or aromatic diaminesand includes diamines containing other hetero atoms. One or more otherdiamines may be used. Examples of diamines include aliphatic diaminessuch as trimethylenediamine, tetramethylenediamine,pentamethylenediamine, hexamethylenediamine,2,2,4-trimethylhexamethylenediamine,2,4,4-trimethylhexamethylenediamine, octamethylenediamine andnonamethylenediamine; and an alicyclic diamine such asbis(4-aminocyclohexyl)methane andbis(4-amino-3-methylcyclohexyl)methane; aromatic diamines, for example,phenylenediamine, diaminotoluene, 2,4-diaminomesitylene,3,5-diethyl-2,6-diaminotoluene, xylylenediamine (in particular,metaxylylenediamine, paraxylylenediamine), bis(2-aminoethyl)benzene,biphenylenediamine, a diamine having a biphenyl backbone (e.g.,4,4′-diamino-3,3′-ethylbiphenyl), adiamine having adiphenyl alkanebackbone [e.g., diaminodiphenylmethane,bis(4-amino-3-ethylphenyl)methane, bis(4-amino-3-methylphenyl)methane,3,3′-dichloro-4,4′-diaminodiphenylmethane,2,2′-bis(4-aminophenyl)propane], bis(4-aminophenyl)ketone,bis(4-aminophenyl)sulfone, or 1,4-naphthalenediamine, and anN-substituted aromatic diamine thereof; alicyclic diamine such as1,3-cyclopentanediamine, 1,4-cyclohexanediamine, andbis(4-amino-3-methylcyclohexyl)methane; an aliphatic amine, such astrimethylenediamine, tetramethylenediamine, pentamethylenediamine,hexamethylenediamine, 2,2,4-trimethylhexamethylenediamine,2,4,4-trimethylhexamethylenediamine, and octamethylenediamine, and anN-substituted aliphatic diamine thereof; and ether diamines such aspoly(alkylene ether)diamines including poly(ethylene ether)diamine,poly(propylene ether)diamine, poly(tetramethylene ether)diamine; randomor block copolymers of ethylene oxide and propylene oxide includingpropylene oxide and poly(propylene oxide) terminated poly(ethyleneether)diamine, 4,4′-oxydianiline; and aminated random or blockcopolymers of tetrahydrofuran with minor amounts of a second monomersuch as ethylene oxide, propylene oxide, methyl tetrahydrofuran,bis[4-(3-aminophenoxy)phenyl]methane,bis[4-(4-aminophenoxy)phenyl]methane,1,1-bis[4-(3-aminophenoxy)phenyl]ethane,1,1-bis[4-(4-aminophenoxy)phenyl]ethane,1,2-bis[4-(3-aminophenoxy)phenyl]ethane,1,2-bis[4-(4-aminophenoxy)phenyl]ethane,2,2-bis[4-(3-aminophenoxy)phenyl]propane,2,2-bis[4-(4-aminophenoxy)phenyl]propane,2,2-bis[4-(3-aminophenoxy)phenyl]butane,2,2-bis[4-(4-aminophenoxy)phenyl]butane,2,2-bis[4-(3-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane,2,2-bis[4-(4-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane,4,4′-bis(3-aminophenoxy)biphenyl, 4,4′-bis(4-aminophenoxy)biphenyl,bis[4-(3-aminophenoxy)phenyl] ketone, bis[4-(4-aminophenoxy)phenyl]ketone, bis[4-(3-aminophenoxy)phenyl] sulfide,bis[4-(4-aminophenoxy)phenyl] sulfide, bis[4-(3-aminophenoxy)phenyl]sulfone and bis[4-(4-aminophenoxy)phenyl] sulfone.

Any suitable dianhydride or dianhydride combination can be used to makethe copoly(imide oxetane) and one or more dianhydrides can be used.Aliphatic and aromatic dianhydrides can find application in making thecopoly(imide oxetane)s of this invention. Examples of usefuldianhydrides of the present invention include pyromellitic dianhydride(PMDA); 3,3′,4,4′-biphenyl tetracarboxylic dianhydride (BPDA);3,3′,4,4′-benzophenone tetracarboxylic dianhydride (BTDA);4,4′-oxydiphthalic anhydride (ODPA); 3,3′,4,4′-diphenylsulfonetetracarboxylic dianhydride (DSDA);4,4′-(4,4′-isopropylidenediphenoxy)bis(phthalic anhydride) (BPADA);2,3,6,7-naphthalene tetracarboxylic dianhydride; 1,2,5,6-naphthalenetetracarboxylic dianhydride; 1,4,5,8-naphthalene tetracarboxylicdianhydride; 2,6-dichloronaphthalene-1,4,5,8-tetracarboxylicdianhydride; 2,7-dichloronaphthalene-1,4,5,8-tetracarboxylicdianhydride; 2,3,3′,4′-biphenyl tetracarboxylic dianhydride;2,2′,3,3′-biphenyl tetracarboxylic dianhydride; 2,3,3′,4′-benzophenonetetracarboxylic dianhydride; 2,2′,3,3′-benzophenone tetracarboxylicdianhydride; 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride;1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride;1,1-bis(3,4-dicarboxyphenyl)ethane dianhydride;bis(2,3-dicarboxyphenyl)methane dianhydride;bis(3,4-dicarboxyphenyl)methane dianhydride;4,4′-(hexafluoroisopropylidene)diphthalic anhydride (6FDA);bis(3,4-dicarboxyphenyl)sulfoxide dianhydride;tetrahydrofuran-2,3,4,5-tetracarboxylic dianhydride;pyrazine-2,3,5,6-tetracarboxylic dianhydride;thiophene-2,3,4,5-tetracarboxylic dianhydride;phenanthrene-1,8,9,10-tetracarboxylic dianhydride;perylene-3,4,9,10-tetracarboxylic dianhydride;bis-1,3-isobenzofurandione; bis(3,4-dicarboxyphenyl)thioetherdianhydride; bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylicdianhydride;2-(3′,4′-dicarboxyphenyl)5,6-dicarboxybenzimidazole dianhydride;2-(3′,4′-dicarboxyphenyl)5,6-dicarboxybenzoxazole dianhydride;2-(3′,4′-dicarboxyphenyl)5,6-dicarboxybenzothiazole dianhydride;bis(3,4-dicarboxyphenyl)2,5-oxadiazole 1,3,4-dianhydride;2,5-(3′,4′-dicarboxydiphenylether) 1,3,4-oxadiazole dianhydride;butane-1,2,3,4-tetracarboxylic dianhydride;pentane-1,2,4,5-tetracarboxylic dianhydride; cyclobutane tetracarboxylicdianhydride; cyclopentane-1,2,3,4-tetracarboxylic dianhydride;cyclohexane-1,2,4,5 tetracarboxylic dianhydride;cyclohexane-2,3,5,6-tetracarboxylic dianhydride; 3-ethylcyclohexane-3-(1,2)5,6-tetracarboxylic dianhydride; 1-methyl-3-ethylcyclohexane-3-(1,2)5,6-tetracarboxylic dianhydride; 1-ethylcyclohexane-1-(1,2),3,4-tetracarboxylic dianhydride;1-propylcyclohexane-1-(2,3),3,4-tetracarboxylic dianhydride;1,3-dipropylcyclohexane-1-(2,3),3-(2,3)-tetracarboxylic dianhydride;dicyclohexyl-3,4,3′,4′-tetracarboxylic dianhydride; 4,4′-bisphenol Adianhydride; 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride;bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylicdianhydride;hydroquinonediphthalic anhydride; ethyleneglycol bis(trimelliticanhydride); 9,9-bis-(trifluoromethyl)xanthenetetracarboxylic dianhydride(6FCDA); 9-phenyl-9-(trifluoromethyl)xanthenetetracarboxylic dianhydride(3FCDA); 9,9-diphenyl-2,3,6,7-xanthenetetracarboxylic dianhydride(PPXDA); 9,9-diphenyl-2,3,6,7-tetramethylxanthene (TMPPX);9,9-diphenyl-2,3,6,7-xanthenetetracarboxylic bis(p-anisidylimide);9,9-diphenyl-2,3,6,7-xanthenetetracarboxylic bis(butylimide);9,9-diphenyl-2,3,6,7-xanthenetetracarboxylic bis(p-tolylimide);9-phenyl-9-methyl-2,3,6,7-xanthenetetracarboxylic dianhydride (MPXDA);9-phenyl-9-methyl-2,3,6,7-xanthenetetracarboxylic bis(propylimide);9-phenyl-9-methyl-2,3,6,7-xanthenetetracarboxylic bis(p-tolylimide);9,9-dimethyl-2,3,6,7-xanthenetetracarboxylic dianhydride (MMXDA);9,9-dimethyl-2,3,6,7-xanthenetetracarboxylic bis(propylimide);9,9-dimethyl-2,3,6,7-xanthenetetracarboxylic bis(tolylimide);9-ethyl-9-methyl-2,3,6,7-xanthenetetracarboxlylic dianhydride (EMXDA);9,9-diethyl-2,3,6,7-xanthenetetracarboxylic dianhydride (EEXDA); etc.Many of the above mentioned dianhydrides (if not all) can also be usedin their ‘tetra-acid form’ (or as mono, di, tri, or tetra esters of thetetra acid), or as their diester acid halides (chlorides). In someembodiments of the present invention however, the dianhydride form isgenerally preferred because it is generally more reactive than the acidor the ester.

Typically the reaction is conducted in the presence of one or moreorganic solvents for the dianydride and diamine. Exemplary solventsinclude N,N-dimethylformamide, N,N-dimethylacetamide,N,N-diethylacetamide, N,N-dimethylmethoxyacetamide,N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone,N-methylcaprolactam, 1,2-dimethoxyethane, bis(2-methoxyethyl) ether,1,2-bis(2-methoxyethoxy)ethane, bis[2-(2-methoxyethoxy)ethyl] ether,tetrahydrofuran, 1,3-dioxane, 1,4-dioxane, pyridine, picoline,dimethylsulfoxide, dimethylsulfone, tetramethylurea andhexamethylphosphoramide. The reaction temperature is normally betweenabout 15° C. and 75° C., preferably less than about 50° C. The reactioncan be carried out under any pressure and ambient pressure issatisfactory. The reaction is typically conducted under any dry inertatmosphere such as nitrogen, helium, and argon. The reaction timedepends upon the reactive nature of the reactants, solvent and reactiontemperature. The reaction is usually continued for sufficient time tocomplete formation of a copoly(amic acid oxetane) which is usually fromabout 0.1 to 50 hours, say, about 2 to 30 hours. The copoly(amic acidoxetane) can be thermally imidized, resulting in the evolution of water,by heating, e.g. at a temperature of at least about 120° C., and oftenfrom about 150° C. to 400° C., or chemically imidized.

FOX Diamines

The FOX diamines used in making the copoly(imide oxetane)s of thisinvention can be represented by the structureNH₂—R¹—C(O)—O-J-C(O)—R¹—NH₂where J, R¹, R², R³ and m are as defined above.

One source of FOX diamines uses fluorine-containing oxetane oligomerswhere the oligomers are functionalized to provide the diamine. Thefunctionalization may proceed by any suitable process. A particularlyadvantageous process is to react hydroxyl-terminated oligomer with anacyl reagent containing a nitro substituent under nucleophilic reactionconditions to provide a di-nitro functionalized oligomer. The di-nitrofunctionalized oligomer can be readily hydrogenated under hydrogenationconditions, especially mild hydrogenation conditions, to provide the FOXdiamine.

The hydroxyl-terminated fluorine containing oxetane oligomers can berepresented by the structure:H—O-J-Hwhere J is as defined above. Examples of the oligomers include, but arenot limited to, oligomers made from one or more of3-(2,2,2-trifluoroethoxymethyl)-3-(2,2,3,3,4,4,4-heptafluorobutoxymethyl)-oxetane,3-(2,2,2-trifluoroethoxymethyl)-3-(3,3,4,4,5,5,6,6,7,7,8,8,8-trifluorooctyloxymethyl)oxetane,3-(2,2,3,3,4,4,4-heptafluoro-butoxymethyl)-3-(2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-pentadecafluorooctyloxymethyl)oxetane,3-(2,2,2-trifluoroethoxymethyl)-3-(3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluoro-decyloxymethyl)oxetaneand3-(2,2,3,3,4,4,4-heptafluorobutoxymethyl)-3-(3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,12,12,12-heneicosafluorodedecyloxymethyl)oxetane,and block oligomers with diols and hydroxyl-terminated oligomers such asethylene glycol, propylene glycol, 1,3-propanediol, butanediol,poly(alkylene ethers) including poly(ethylene ether), poly(propyleneether), poly(tetramethylene ether); random or block copolymers ofethylene oxide and propylene oxide including propylene oxide andpoly(propylene oxide), random or block copolymers of tetrahydrofuranwith minor amounts of a second monomer such as ethylene oxide, propyleneoxide, methyl tetrahydrofuran, bis[4-(3-hydroxyphenoxy)phenyl]methane,bis[4-(4-hydroxyphenoxy)phenyl]methane,1,1-bis[4-(3-hydroxyphenoxy)phenyl]ethane,1,1-bis[4-(4-hydroxyphenoxy)phenyl]ethane,1,2-bis[4-(3-hydroxyphenoxy)phenyl]ethane,1,2-bis[4-(4-hydroxyphenoxy)phenyl]ethane,2,2-bis[4-(3-hydroxyphenoxy)phenyl]propane,2,2-bis[4-(4-hydroxyphenoxy)phenyl]propane,2,2-bis[4-(3-hydroxyphenoxy)phenyl]butane,2,2-bis[4-(4-hydroxyphenoxy)phenyl]butane,2,2-bis[4-(3-hydroxyphenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane,2,2-bis[4-(4-hydroxyphenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane,4,4′-bis(3-hydroyphenoxy)biphenyl, 4,4′-bis(4-hysroxyphenoxy)biphenyl,bis[4-(3-hydroxyphenoxy)phenyl] ketone, bis[4-(4-hydrosyphenoxy)phenyl]ketone, bis[4-(3-hysroxyphenoxy)phenyl] sulfide,bis[4-(4-hydroxyphenoxy)phenyl] sulfide, bis[4-(3-hydroxyphenoxy)phenyl]sulfone and bis[4-(4-hydroxyphenoxy)phenyl] sulfone.

The nucleophilic reaction conditions to convert a hydroxyl-terminatedoxetane oligomer to a di-nitro functionalized oligomer can vary widelyand optimal conditions will depend upon the acyl reagent used. The acylreagent is generally present in a stoichiometric excess of that requiredfor the nucleophilic reaction with both hydroxyls of the oligomer, say,a mole ratio of acyl reagent to hydroxyl on the oligomer of betweenabout 1.1:1 to 10:1, and most often between about 1.5:1 to 5:1.Typically the reactions are conducted in the presence of one or moreorganic solvents for the oligomer and a base. The solvent and the basemay be the same or different. Advantageously the base is an organicamine. The base is preferably present in an amount in excess of thatrequired to neutralize the co-product of the nucleophilic reaction.Often the mole ratio of base to acyl reagent is at least about 2:1, andmore frequently in the range of about 5:1 to 50:1. The reactiontemperature is normally between about 10° C. and 120° C., preferablyabout 30° C. to 80° C. Preferably the reaction menstruum is understirring and the acyl reagent is gradually added to avoid undueexotherms. The reaction can be carried out under any pressure andambient pressure is satisfactory. The reaction is typically conductedunder any dry inert atmosphere such as nitrogen, helium, and argon. Thereaction time depends upon the reactive nature of the reactants, solventand reaction temperature. Usually the reaction is complete in about 0.01to 20 hours.

Exemplary bases that can serve as solvents include trimethylamine,triethylamine, tripropylamine, tributylamine, N,N-dimethylformamide,N,N-dimethylacetamide, N,N-diethylacetamide,N,N-dimethylmethoxyacetamide. Other solvents include ethanol,n-propanol, isobutanol, butanol, hexanol, cyclohexanol, cyclohexane,hexane, benzene, toluene, xylene, methylene chloride, ethylenedichloride, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone,N-methylcaprolactam, 3-methylphenol, 1,2-dimethoxyethane,bis(2-methoxyethyl) ether, 1,2-bis(2-methoxyethoxy)ethane,bis[2-(2-methoxyethoxy)ethyl] ether, tetrahydrofuran, 1,3-dioxane,1,4-dioxane, pyridine, picoline, dimethylsulfoxide, dimethylsulfone,tetramethylurea and hexamethylphosphoramide.

The acyl reagent is preferably an acyl halide such as a bromide,chloride or iodide with chlorides being most preferred. Examples ofnitro-substituted acyl reagents include, without limitation,3-nitrobenzaldehyde, 3, nitrobenzoic acid, methyl 3-nitrobnzoate,3-nitrobenzoyl chloride, 4-nitrobenzoyl chloride, 3-nitrobenzoylbromide, 4-nitrobenzoyl bromide, 3-nitrobenzoyl iodide, 4-nitrobenzoyliodide, nitroacetyl bromide, nitroacetyl chloride, nitroacetyl iodide,nitropropionyl chloride, nitrobutyryl chloride, nitrovaleryl chloride,nitrocaproyl chloride, and isomers and lower alkyl and halo-substitutedcompounds thereof.

The dinitro-functionalized oligomer is then subjected to hydrogenationto convert the nitro groups to amino groups. As the nitro groups arereadily hydrogenated to amino groups, mild hydrogenations conditions canbe used to prevent undue hydrogenation of other moieties in theoligomer. The hydrogenation is typically conducted in a solvent whichmay be the same or different from the solvent used in the nitrofunctionalization of the oligomers. Often, alkanol solvents arepreferred. The hydrogenation is conducted in the presence of acatalytically effective amount of hydrogenation catalyst. Hydrogenationcatalysts include platinum catalysts, such as, for example,platinum/carbon catalysts (Pt/C) or PtO₂; palladium catalysts, such as,for example, Pd/C; rhodium catalysts, such as, for example, Rh/C,Rh/Al₂O₃ or Rh₂O₃; nickel catalysts, nickel/molybdenum catalysts suchas, for example, Raney nickel; or iridium catalysts, and mixturesthereof. Special preference is given to Pd/C or Rh/C. Frequently thereaction menstruum is maintained under mixing such as stirring oragitation when conducted in a batch process. The hydrogenationtemperature is usually in the range of about 10° C. to 120° C.,preferably about 20° C. to 80° C. Hydrogen is provided at a pressure ofbetween about 100 and 5000 kPa gauge, preferably between about 150 and1000 kPa gauge. The duration of the reaction in batch mode is generallyin the range of about 0.5 to 40 hours. In continuous processes, thereaction menstruum passes through a fixed catalyst bed, often at aliquid hourly space velocity of between about 0.5 and 10 hr⁻¹.

EXAMPLES

The following examples are to further illustrate the invention and arenot in limitation thereof. All parts and percentages are by mass unlessotherwise stated or clear from their context.

Example 1: Synthesis of Dinitro-Terminated Oxetane Oligomer

This example uses a hydroxyl-terminated oxetane available as POLYFOX™PF-6320,3-(2,2,2-trifluoroethoxymethyl)-3-(2,2,3,3,4,4,4-heptafluorobutoxymethyl)-oxetaneoligomer having an approximate molecular weight of 3400 g/mole. To aglass flask blanketed with nitrogen which contains about 150 millilitersof toluene are charged 60.32 grams of the oligomer. Triethyl amine(14.52 grams) is added and the solution is stirred for about 10 minutesand heated to about 50° C. A previously prepared solution of 10.4 gramsof p-nitrobenzoyl chloride dissolved in 150 milliliters of toluene isadded to the oligomer-containing solution drop wise over a period ofabout 30 minutes. The solution is then stirred under reflux for about 16hours, then cooled to room temperature. The solution is then filtered,washed twice (250 milliliters) with an aqueous solution of 5 masspercent sodium bicarbonate and then once with 250 milliliters ofdeionized, distilled water. Thereafter the solution is dried overmagnesium sulfate. The liquor is then rotary evaporated to yield aviscous, honey-colored oil. The oil is vacuumed dried. The dried samplecontains the dinitro-terminated oxetane oligomer.

Example 2: Synthesis of Diamine-Terminated Oxetane Oligomer

A 100 milliliter, mechanically stirred, glass reaction vessel is chargedwith 8.8 grams of the dinitro-terminated oxetane oligomer of Example 1,0.445 grams of palladium on carbon hydrogenation catalyst available fromAldrich Chemical Co. having a metal loading of 5 mass percent, and 40milliliters of anhydrous ethanol. The resulting solution is degassed andsubsequently backfilled with hydrogen to 200 kPa gauge. The solution ismaintained under agitation for 16 hours. After removing hydrogen, thesolution is filtered through diatomaceous earth (CELITE™ available fromCelite Corporation, Goleta, Calif., United States) followed by rotaryevaporation and vacuum drying. The dried sample contains the diamine ofthe oxetane oligomer.

Example 3: Synthesis of Copoly(Imide Oxetane)

A series of copoly(imide oxetane)s are prepared using the followinggeneral procedure:

-   -   1. The diamine-terminated oxetane oligomer is dissolved in        N,N-dimethylacetamide to provide an oligomer solution.    -   2. The other diamine, 4,4′-oxydianiline, is added to a stirred,        glass reaction flask and dissolved in N,N-dimethylacetamide.    -   3. An amount of the oligomer solution is added to the flask to        provide a sought mass ratio of the oxetane oligomer to the        diamine.    -   4. The solution in the flask is stirred for about 10 minutes and        then dianhydride, 3,3′,4,4′-bisphenyltetracarboxylic        dianhydride, is added to the flask. The amount of dianhydride        added provides a molar ratio of dianydride to total diamine of        about 1.0:0.95. Sufficient N,N-dimethylacetamide is added to        provide a 20 mass percent solids solution.    -   5. The solution is stirred at ambient temperature (about 22° C.)        for about 16 hours under an inert gas atmosphere.

The solution contains copoly(amic acid oxetane). Table I summarizes thepolymers made.

Example 4: Imidization to Copoly(Imide Oxetane)

Imidization of the polymer material is done using the following generalprocedure. Samples of each solution made in Example 3 are centrifuged toremove gas bubbles. A film is cast from each sample using a doctor bladeto an approximate thickness of about 500 to 750 microns on glass andeach film is placed in a forced air drying chamber at room temperaturefor about 24 to 48 hours to remove solvent and provide a tack-freesurface. Some of the films are then thermally imidized under nitrogenusing a cure cycle with stages at 150° C., 175° C., 200° C. and 250° C.with a minimum hold of 40 minutes at each stage.

Some of the copoly(amic acid oxetane) solutions are chemically imidizedby reaction with acetic anhydride and pyridine. In this procedure, 33.02grams of a 10 mass percent solids copoly(amic acid oxetane) andN,N-dimethylacetamide solution are poured into a 100 milliliter 3-neckedround bottomed flask. Then 3.9 milliliters of pyridine and 3.3milliliters of acetic anhydride are added to the flask and the reactionmixture is mechanically stirred overnight under an inert atmosphere.After about 16 hours the reaction mixture is poured into a blendercontaining water resulting in precipitation of the chemically imidizedcopoly(imide oxetane) product. The copoly(imide oxetane) is filtered,stirred in hot water for several hours, filtered again and allowed todry.

Example 5: Evaluation of Copoly(Imide Oxetane)

The cast and imidized coatings are evaluated for various characteristicsand performance properties.

Modulus of the coatings is determined using a Sintech 2W test frame witha crosshead speed of 5.08 millimeters per minute and analyzed usingTestworks 8.0 software (both available from MTS Systems Corporation,Eden Prairie, Minn., United States). See Table I.

A ThermoFisher ESCA lab 250 X-ray photoelectron spectrometer (availablefrom Thermofisher Scientific, Waltham, Mass., United States) is used forXPS analysis.

A FTA 1000B contact angle goniometer available from First Ten Angstroms,Inc., Portsmouth, Va., United States is used to measure the watercontact angle with an 8 microliter drop being used. See Table I.

Dust adhesion is evaluated by adhering a 6 millimeter diameter sample ofthe cast film on the end of a sonication device. The surface is coatedwith an approximate monolayer of particles having a particle diameter ofless than about 30 microns. The sonication device uses a series ofsonication steps of increasing magnitude.

With respect to dust adhesion, the copoly(imide oxetane)-containingfilms exhibit improved surface clearance and potentially lower adhesionvalues than the homopolymer.

The XPS surface analysis indicates that the fluorine population of theexterior (air-facing) surface of the coating films reaches a plateau ata low fluorine-containing oxetane moiety content in the copoly(imideoxetane) material. The data are presented in Table I. For sake ofcomparison, the fluorine atomic concentration of the oxetane oligomer isabout 29 atomic percent. The interior surface (glass-facing surface) hasa fluorine population higher than that of the bulk, but less than thatof the exterior surface (air-facing surface) which is also reported inTable I. The XPS analysis thus confirms an unexpected migration of thefluorine-containing oxetane moieties in the copoly(imide oxetane) to thesurface, and further indicates that only a very small amount of theoxetane oligomer is required to provide sought low surface energies.Although the presence of the oxetane oligomer does not unduly adverselyaffect the mechanical properties of the copoly(imide oxetane) atsomewhat higher levels, the ability to achieve the low surface energieswith very small amounts of the oxetane oligomer would not detract fromthe desirable bulk properties of the copoly(imide oxetane) material.

TABLE I Diamine Exterior Glass oxetane Surface Surface oligomer, massBreak Stress, Elongation at Water Contact Fluorine, Fluorine, % Modulus,MPa MPa Break, % Angle, ° Atomic % Atomic % 0 3590 141 10.1 81 5 2 0.013560 142 8.3 93 0.1 3570 142 9.2 95 14 5 0.2 3510 139 11.5 95 14 0.43450 138 7.5 94 20 0.5 3350 142 5.5 94 16 9 0.8 3460 138 11.2 94 17 1.03440 141 8.7 98 19 8 2.0 3380 138 8.7 94 17 5.0 3140 126 9.7 95 18 4

What is claimed:
 1. A copoly(imide oxetane) having the structurerepresented by:-(G-M)-(D-M)- wherein: G is represented by the formula═N—R¹—C(O)—O-J-C(O)—R¹—N═ wherein: J is [CH₂—CR²R³—CH₂—O]_(m) or[(CH₂—CR²R³—CH₂—O)_(p)—(R⁶—O)_(q)—(CH₂—CR²R³—CH₂—O)_(r)] wherein R⁶ issubstituted or unsubstituted aliphatic or aromatic moiety of 2 to 16carbons; R¹ is aliphatic or aromatic hydrocarbon moiety of 1 to 10carbon atoms; R² is —H, —F, or alkyl of 1 to 6 carbon atoms; R³ is —F,—R⁴H_((n-a))F_(a), —R⁵—O—R⁴H_((n-a))F_(a), and —O—R⁴H_((n-a))F_(a),wherein R⁴ is an alkyl or ether moiety of 1 to 30 carbons, R⁵ is analkyl moiety of 1 to 30 carbons, a is an integer of 3 to n, and n istwice the number of carbon atoms in the alkyl moiety plus 1; and m isbetween about 4 and 500, p is between about 4 and 150, q is betweenabout 1 and 150, and r is an integer; M is represented by the formula(—C(O))₂-L-(C(O)—)₂ wherein: L is a hydrocarbyl-containing moiety of 2to 100 carbon atoms optionally containing divalent radicals selectedfrom the group consisting of oxygen, silyl, sulfur, carbonyl, sulfonyl,phosphonyl, perfluoro, tertiary amino, and imido; D is represented bythe formula═N—Z—N═ wherein: Z is a hydrocarbyl-containing moiety of 1 to 100 carbonatoms optionally containing divalent radicals selected from the groupconsisting of oxygen, sulfur, silyl, carbonyl, sulfonyl, phosphonyl,perfluoro, tertiary amino, and imido.
 2. The copoly(imide oxetane) ofclaim 1 wherein the omega carbon of R⁴ has three fluoride substituentsand wherein m is between 6 and
 100. 3. The copoly(imide oxetane) ofclaim 2 containing 0.002 to 15 mass percent of G.
 4. The copoly(imideoxetane) of claim 3 which is a block co-polymer.
 5. The copoly(imideoxetane) of claim 3 which is a random co-polymer.
 6. A coating having anouter surface and a bonding surface comprising the copoly(imide oxetane)of claim 1, said coating having an anisotropic distribution of fluorineatoms over its thickness with a higher concentration at the outersurface.
 7. The coating of claim 6 having a water contact angle of atleast 90° at the outer surface.
 8. A method for coating a substrate withthe copoly(imide oxetane) of claim 1, the method comprising applying onthe substrate a solution containing a copoly(amic acid oxetane) havingthe structure represented by:-(G-A)-(D-A)- wherein: G is represented by the formula—NH—R¹—C(O)—O-J-C(O)—R¹—HN— wherein: J is [CH₂—CR²R³—CH₂—O]_(m) or[(CH₂—CR²R³—CH₂—O)_(p)—(R⁶—O)_(q)—(CH₂—CR²R³—CH₂—O)_(r)] wherein R⁶ issubstituted or unsubstituted aliphatic or aromatic moiety of 2 to 16carbons; R¹ is aliphatic or aromatic hydrocarbon moiety of 1 to 10carbon atoms; R² is —H, —F, or alkyl of 1 to 6 carbon atoms; R³ is —F,—R⁴H_((n-a))F_(a), —R⁵—O—R⁴H_((n-a))F_(a), and —O—R⁴H_((n-a))F_(a),wherein R⁴ is an alkyl or ether moiety of 1 to 30 carbons, R⁵ is analkyl moiety of 1 to 30 carbons, a is an integer of 3 to n, and n istwice the number of carbon atoms in the alkyl moiety plus 1; and m isbetween about 4 and 500, p is between about 4 and 150, q is betweenabout 1 and 150, and r is an integer; A is represented by the formula

wherein: L is a hydrocarbyl-containing moiety of 2 to 100 carbon atomsoptionally containing divalent radicals selected from the groupconsisting of oxygen, silyl, sulfur, carbonyl, sulfonyl, phosphonyl,perfluoro, tertiary amino, and imido; D is represented by the formula—NH—Z—NH— wherein: Z is a hydrocarbyl-containing moiety of 1 to 100carbon atoms optionally containing divalent radicals selected from thegroup consisting of oxygen, sulfur, silyl, carbonyl, sulfonyl,phosphonyl, perfluoro, tertiary amino, and imido; in a volatile solventto form a copoly(amic acid oxetane) coating, and subjecting thecopoly(amic acid oxetane) coating to drying and imidization conditionsto form the anisotropic copoly(imide oxetane) coating.
 9. A polymercomposite comprising a copolymer containing the copoly(imide oxetane) ofclaim 1 and a particulate filler, wherein the polymer composite has awater contact angle of at least 100°.
 10. An article of manufacturecomprising a polymeric matrix and the copoly(imide oxetane) of claim 1,said article having an outer surface, and said article of manufacturehaving a higher concentration of fluorine atoms at the outer surfacethan that of the polymeric matrix without the copoly(imide oxetane). 11.The article of manufacture of claim 10 which is a cast article ofmanufacture.
 12. The article of manufacture of claim 10 which is amolded article of manufacture.
 13. A method for making the article ofmanufacture of claim 10 comprising W forming the polymeric matrixcontaining comprising a copoly(amic acid oxetane) having the structurerepresented by:-(G-A)-(D-A)- wherein: G is represented by the formula—NH—R¹—C(O)—O-J-C(O)—R¹—HN— wherein: J is [CH₂—CR²R³—CH₂—O]_(m) or[(CH₂—CR²R³—CH₂—O)_(p)—(R⁶—O)_(q)—(CH₂—CR²R³—CH₂—O)_(r)] wherein R⁶ issubstituted or unsubstituted aliphatic or aromatic moiety of 2 to 16carbons; R¹ is aliphatic or aromatic hydrocarbon moiety of 1 to 10carbon atoms; R² is —H, —F, or alkyl of 1 to 6 carbon atoms; R³ is —F,—R⁴H_((n-a))F_(a), —R⁵—O—R⁴H_((n-a))F_(a), and —O—R⁴H_((n-a))F_(a),wherein R⁴ is an alkyl or ether moiety of 1 to 30 carbons, R⁵ is analkyl moiety of 1 to 30 carbons, a is an integer of 3 to n, and n istwice the number of carbon atoms in the alkyl moiety plus 1; and m isbetween about 4 and 500, p is between about 4 and 150, q is betweenabout 1 and 150, and r is an integer; A is represented by the formula

wherein: L is a hydrocarbyl-containing moiety of 2 to 100 carbon atomsoptionally containing divalent radicals selected from the groupconsisting of oxygen, silyl, sulfur, carbonyl, sulfonyl, phosphonyl,perfluoro, tertiary amino, and imido; D is represented by the formula—NH—Z—NH— wherein: Z is a hydrocarbyl-containing moiety of 1 to 100carbon atoms optionally containing divalent radicals selected from thegroup consisting of oxygen, sulfur, silyl, carbonyl, sulfonyl,phosphonyl, perfluoro, tertiary amino, and imido; into a first articlehaving an outer surface and (2) subjecting the first article toimidization conditions to form the article of manufacture comprising thecopoly(imide oxetane).
 14. The method of claim 13 wherein the article ofmanufacture is a cast article of manufacture.
 15. The method of claim 13wherein the article of manufacture is a molded article.
 16. The methodof claim 15 wherein the molded article is produced from dry polymericmatrix particles comprising the copoly(amic acid oxetane) and formedinto the shape of the article under pressure and imidization conditions.17. A method for making the article of manufacture of claim 10comprising (1) forming a polymeric matrix comprising a copoly(amic acidoxetane) into a first article having an outer surface, (2) contactingthe outer surface with at least one of (i) at least one diamine oligomerrepresented by the formula:(E)^(y)R¹—C(O)—O-J-C(O)—R¹(E)_(y) wherein: J is [CH₂—CR²R³—CH₂—O]_(m) or[(CH₂—CR²R³—CH₂—O)_(p)—(R⁶—O)_(q)—(CH₂—CR²R³—CH₂—O)_(r)] wherein R⁶ issubstituted or unsubstituted aliphatic or aromatic moiety of 2 to 16carbons; E is —NH₂; y is 1 or 2; R¹ is aliphatic or aromatic hydrocarbonmoiety of 1 to 10 carbon atoms; R² is —H, —F, or alkyl of 1 to 6 carbonatoms; R³ is —F, —R⁴H_((n-a))F_(a), —R⁵—O—R⁴H_((n-a))F_(a), and—O—R⁴H_((n-a))F_(a), wherein R⁴ is an alkyl or ether moiety of 1 to 30carbons and the omega carbon of R⁴ has three fluoride substituents, R⁵is an alkyl moiety of 1 to 30 carbons, a is an integer of 3 to n, and nis twice the number of carbon atoms in the alkyl moiety plus 1; and m isbetween about 6 and 100, p is between about 4 and 150, q is betweenabout 1 and 150, and r is an integer, and (ii) at least one copoly(amicacid oxetane) having the structure represented by:-(G-A)-(D-A)- wherein: G is represented by the formula—NH—R¹—C(O)—O-J-C(O)—R¹—HN— wherein: J is [CH₂—CR²R³—CH₂—O]_(m) or[(CH₂—CR²R³—CH₂—O)_(p)—(R⁶—O)_(q)—(CH₂—CR²R³—CH₂—O)_(r)] wherein R⁶ issubstituted or unsubstituted aliphatic or aromatic moiety of 2 to 16carbons; R¹ is aliphatic or aromatic hydrocarbon moiety of 1 to 10carbon atoms; R² is —H, —F, or alkyl of 1 to 6 carbon atoms; R³ is —F,—R⁴H_((n-a))F_(a), —R⁵—O—R⁴H_((n-a))F_(a), and —O—R⁴H_((n-a))F_(a),wherein R⁴ is an alkyl or ether moiety of 1 to 30 carbons, R⁵ is analkyl moiety of 1 to 30 carbons, a is an integer of 3 to n, and n istwice the number of carbon atoms in the alkyl moiety plus 1; and m isbetween about 4 and 500, p is between about 4 and 150, q is betweenabout 1 and 150, and r is an integer; A is represented by the formula

wherein: L is a hydrocarbyl-containing moiety of 2 to 100 carbon atomsoptionally containing divalent radicals selected from the groupconsisting of oxygen, silyl, sulfur, carbonyl, sulfonyl, phosphonyl,perfluoro, tertiary amino, and imido; D is represented by the formula—NH—Z—NH— wherein: Z is a hydrocarbyl-containing moiety of 1 to 100carbon atoms optionally containing divalent radicals selected from thegroup consisting of oxygen, sulfur, silyl, carbonyl, sulfonyl,phosphonyl, perfluoro, tertiary amino, and imido, to produce a secondarticle, and (3) subjecting the second article to imidization conditionsto form the article of manufacture comprising the poly(imide oxetane).